CN112939091B - Double-modified lithium manganate material and preparation method thereof - Google Patents

Double-modified lithium manganate material and preparation method thereof Download PDF

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CN112939091B
CN112939091B CN202110137405.XA CN202110137405A CN112939091B CN 112939091 B CN112939091 B CN 112939091B CN 202110137405 A CN202110137405 A CN 202110137405A CN 112939091 B CN112939091 B CN 112939091B
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lithium manganate
double
manganate material
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coating layer
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CN112939091A (en
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王圣贤
谢芳
苗力孝
刘天雷
牛庆荣
崔云龙
刘如雷
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Shandong Haike Innovation Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
    • C01F5/12—Magnesia by thermal decomposition of magnesium compounds by thermal decomposition of magnesium sulfate, with or without reduction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C01F7/308—Thermal decomposition of nitrates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a double-modified lithium manganate material and a preparation method thereof, belonging to the field of anode materials. The double-modified lithium manganate material has metal element doping in a bulk phase, a metal oxide coating layer on the surface, and a carbon coating layer between the metal oxide coating layer and a main body material; the doping amount of the metal element is 1000ppm-10000ppm. The invention is applied to the aspect of lithium ion battery anode materials, solves the technical problem that doped elements existing in the existing one-step method for doping and coating lithium manganate are not uniformly distributed in a bulk phase, and has the characteristics of simple and efficient preparation process, capability of obtaining the double-modified lithium manganate material by one step, realization of industrial production, uniform distribution of the doped elements in the bulk phase, effective improvement of cycle stability and guarantee of material capacity.

Description

Double-modified lithium manganate material and preparation method thereof
Technical Field
The invention belongs to the field of positive electrode materials, and particularly relates to a double-modified lithium manganate material and a preparation method thereof.
Background
The performance of the positive electrode material, which is an important component of the lithium ion battery, largely determines the energy density and power density of the lithium ion battery. The lithium manganate anode material has the advantages of high platform voltage, low cost, safety, environmental protection, no toxicity and the like, and has a wide application prospect. However, in the long-cycle process, the lithium manganate material is easy to generate J-T effect, and the induced lattice distortion causes structural phase change; mn (Mn) 3+ Disproportionation reaction to produce Mn 2+ And manganese is dissolved under the corrosion of the electrolyte, so that the cycle performance of the material is greatly deteriorated.In order to solve the above problems, modification measures such as doping and coating are usually applied to improve the cycling stability of the material. However, although the doped metal element can effectively inhibit J-T distortion, the doped metal element cannot inhibit manganese dissolution of the material; although the coating can effectively inhibit the corrosion of the electrolyte, the coating is not enough to maintain the structural stability in the long-circulating process, and meanwhile, the coating has a certain ion insulation effect and can also cause the loss of the material capacity. Therefore, single element doping or single-layer coating cannot effectively solve the above problems, and therefore, double modification of the material by utilizing the synergistic effect of doping and coating is an effective technical route. At present, a doping-coating double-modification method for a positive electrode material needs two steps, namely doping the material and then coating the material. The method has complex process, time consumption and high cost, so that an efficient and simple preparation method of the double modified material is needed to be developed.
Chinese patent CN105576218B discloses a method for double modification of lithium manganate by doping and coating in one step, wherein in the product obtained by the method of the present invention, part of aluminum in the aluminum source on the surface of manganous oxide enters the lithium manganate at the outer layer to form LiMn2-xAlxO4 solid solution during the heat treatment process, and the rest of aluminum exists in the form of oxide, so that the lithium manganate is modified by double functions of coating and doping. The aluminum oxide layer can effectively prevent lithium manganate from being in direct contact with the electrolyte; the LiMn2-xAlxO4 solid solution has a more stable structure than LiMn2O4 without obstructing the passage of lithium ions. The double-function modification effectively inhibits the dissolution of divalent manganese and improves the cycle performance and high-temperature performance of lithium manganate.
However, the above method realizes doping and cladding double modification of the material by controlling the calcination temperature so that part of the metal elements in the metal oxide diffuses into the bulk of the material, and this method has a problem that the distribution of the doped elements in the bulk phase is not uniform.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the technical problem that the doping elements in the lithium manganate are not uniformly distributed in the bulk phase in the existing one-step method for doping and coating the lithium manganate, and provides a double-modified lithium manganate material and a preparation method thereof, wherein the preparation process is simple and efficient, the double-modified lithium manganate material can be obtained by only one step, the industrial production can be realized, the distribution of the doping elements in the bulk phase is uniform, the circulation stability is effectively improved, and the material capacity is ensured.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
the invention provides a double-modified lithium manganate material, wherein a metal element is doped in a double-modified lithium manganate material body, a metal oxide coating layer is arranged on the surface of the double-modified lithium manganate material body, and a carbon coating layer is arranged between the metal oxide coating layer and a main body material; the doping amount of the metal element is 1000ppm-10000ppm.
Preferably, the metal element is at least one of Mg, al, cu, zr, ti, zn, fe, ni or Mo; the metal oxide coating layer is MgO or Al 2 O 3 、CuO、ZrO 2 、TiO 2 ZnO, feO, niO or MoO 3 At least one of (a); the carbon coating layer is at least one of soft carbon and hard carbon in amorphous carbon.
Preferably, the content of the metal oxide coating layer is 0.5-5wt% of the lithium manganate material to be coated; the content of the carbon coating layer is 0.2-1wt% of the lithium manganate material to be coated.
The invention also provides a preparation method of the double-modified lithium manganate material in any technical scheme, which comprises the following steps:
preparing an aqueous solution containing lithium, manganese and modified elements in a certain proportion, and marking as a solution A;
preparing a solution of an organic complexing agent with a certain concentration, and marking as a solution B;
adding the solution A into the solution B, and controlling the reaction temperature and the pH value until a gel-like substance is obtained;
drying the gel-like material, ball milling, and adding into N 2 /O 2 And carrying out first-stage calcination and second-stage calcination in a mixed atmosphere to obtain the double-modified lithium manganate material.
Preference is given toThe source of lithium is at least one of lithium acetate, lithium carbonate, lithium hydroxide and lithium nitrate; the source of the manganese is at least one of manganese nitrate, manganese sulfate, manganese carbonate, manganese acetate and manganese oxide; the source of the modified element is MAC and MCO 3 、MOH、MNO 3 、MSO 4 M is Mg, al, cu, zr, ti, zn, fe, ni or Mo, and AC is acetate.
Preferably, the organic complexing agent is at least one of citric acid, oxalic acid, glutamic acid, polyallyl alcohol, PVDF and polyacrylamide.
Preferably, the controlling of the reaction temperature and the pH specifically comprises: controlling the reaction temperature to be 40-100 ℃, and controlling the pH value to be 7-11.
Preferably, said N is 2 /O 2 O in mixed atmosphere 2 The volume ratio of (A) is 0.85-1.0.
Preferably, the calcination temperature of the first stage of calcination is 500-800 ℃, and the calcination time is 6-10h.
Preferably, the calcination temperature of the second stage of calcination is 200-600 ℃, and the calcination time is 3-6h.
Compared with the prior art, the invention has the beneficial effects that:
on one hand, the invention provides a double-modified lithium manganate material, metal element doping is carried out in a bulk phase, the material lattice distortion can be effectively inhibited, the interface stability of the material can be improved by a metal oxide coating layer, the corrosion of electrolyte is reduced, the transmission rate of lithium ions between the metal oxide coating layer and a main material can be accelerated by a carbon coating layer, the material is ensured to have higher capacity and cycling stability, and the conductive carbon coating layer is constructed between the metal oxide coating layer and the main material, so that the cycle stability can be improved, and the capacity of the material can be normally released;
the invention also provides a preparation method of the double-modified lithium manganate material, which has the characteristics of simple and efficient preparation process, capability of obtaining the double-modified lithium manganate material by only one step and realization of industrial production; furthermore, in the preparation process, the organic complexing agent not only serves as a complexing agent to enable metal ions to be uniformly distributed, but also serves as a carbon source to form a carbon coating layer, so that the full utilization of substances is achieved, and the environmental pollution is reduced; the metal element can be directionally induced to form a metal oxide coating layer and a carbon layer on the surface by controlling the calcining atmosphere, so that the synchronous formation of doping-coating is realized, the process steps are reduced, and the synthesis period is shortened.
Drawings
Fig. 1 is a schematic structural diagram of a double-modified lithium manganate material provided in an embodiment of the present invention;
FIG. 2 is a graph showing the cycle performance of a dual-modified lithium manganate material according to an embodiment of the present invention;
in the above figures: 1. a metal element; 2. a metal oxide coating layer; 3. and (3) a carbon coating layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be fully described in detail below with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the general principles of the invention, and are not intended to limit the invention to the precise embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the general idea of the invention, fall within the scope of protection of the invention.
The invention provides a double-modified lithium manganate material, as shown in fig. 1, a metal element 1 is doped in a double-modified lithium manganate material body, a metal oxide coating layer 2 is arranged on the surface of the double-modified lithium manganate material body, and a carbon coating layer 3 is arranged between the metal oxide coating layer 2 and a main body material; the doping amount of the metal element 1 is 1000ppm-10000ppm. Bulk phase doping or surface coating of the conventional modified lithium manganate material is to improve the cycle performance at the cost of sacrificing part of capacity, and the capacity and the cycle stability cannot be well considered. The double-modified lithium manganate material has the advantages that the metal element 1 is doped in the material phase, the material lattice distortion can be effectively inhibited, specifically, the metal ion doping can effectively maintain the average valence state of manganese ions to be more than or equal to +3.5, the Jahn-Teller (J-T) effect is inhibited, the material interface stability can be improved by the metal oxide coating layer 2, the corrosion of electrolyte is reduced, the transmission rate of the lithium ions between the metal oxide coating layer 2 and a main body material can be accelerated by the carbon coating layer 3, the material is ensured to have higher capacity and circulation stability, the conductive carbon coating layer 3 is constructed between the metal oxide coating layer 2 and the main body material, and the capacity of the material can be normally released while the circulation stability is improved. The technical solution specifically defines the doping amount of the metal element 1, and it is understood that the doping amount may also be 2000ppm, 3000ppm, 4000ppm, 5000ppm, 6000ppm, 7000ppm, 8000ppm, 9000ppm and any point value within the range thereof.
In a preferred embodiment, the metal element is at least one of Mg, al, cu, zr, ti, zn, fe, ni or Mo; the metal oxide coating layer is MgO or Al 2 O 3 、CuO、ZrO 2 、TiO 2 ZnO, feO, niO or MoO 3 At least one of; the carbon coating layer is at least one of soft carbon and hard carbon in amorphous carbon. The technical scheme specifically defines the types of the metal element, the metal oxide coating layer and the carbon coating layer, and it can be understood that the types of the metal element, the metal oxide coating layer and the carbon coating layer can be other substances reasonably selected by a person skilled in the art in combination with common knowledge in the field.
In a preferred embodiment, the content of the metal oxide coating layer is 0.5-5wt% of the lithium manganate material to be coated; the content of the carbon coating layer is 0.2-1wt% of the coated lithium manganate material. The content of the metal oxide coating layer and the content of the carbon coating layer are specifically limited in this technical scheme, and it can be understood that the content of the metal oxide coating layer can be any value within the range of 1wt%, 2wt%, 3wt%, 4wt% and the range thereof, and the content of the carbon coating layer can be any value within the range of 0.4wt%, 0.6wt%, 0.8wt% and the range thereof.
The invention also provides a preparation method of the double-modified lithium manganate material in any technical scheme, which comprises the following steps:
preparing an aqueous solution containing lithium, manganese and modified elements in a certain proportion, and marking as a solution A;
preparing a solution of an organic complexing agent with a certain concentration, and marking as a solution B;
adding the solution A into the solution B, and controlling the reaction temperature and the pH value until a gel-like substance is obtained;
drying the gel-like material, ball milling, and adding N 2 /O 2 And carrying out first-stage calcination and second-stage calcination in a mixed atmosphere to obtain the double-modified lithium manganate material.
The traditional preparation of the double-modified lithium manganate material is to modify a finished product of a cathode material, namely the preparation process and the modification process of the finished product material are divided. The process is complicated and the synthesis period is long; in the process of preparing lithium manganate by the traditional sol-gel method, a large amount of organic matters are decomposed and volatilized, so that the environment is polluted, the waste of substances is caused, and the generation cost is very high. The preparation method provided by the technical scheme of the invention has the characteristics that the preparation process is simple and efficient, the double-modified lithium manganate material can be obtained only by one step, and industrial production can be realized; in the preparation process, the organic complexing agent not only serves as a complexing agent to enable metal ions to be uniformly distributed, but also serves as a carbon source to form a carbon coating layer, so that the full utilization of substances is achieved, and the environmental pollution is reduced; the metal element can be directionally induced to be doped to form a metal oxide coating layer and a carbon coating layer on the surface by controlling the calcining atmosphere, so that the synchronous formation of doping and coating is realized, the process steps are reduced, and the synthesis period is shortened.
In a preferred embodiment, the source of lithium is at least one of lithium acetate, lithium carbonate, lithium hydroxide, lithium nitrate; the source of the manganese is at least one of manganese nitrate, manganese sulfate, manganese carbonate, manganese acetate and manganese oxide; the source of the modified element is MAC and MCO 3 、MOH、MNO 3 、MSO 4 M is Mg, al, cu, zr, ti, zn, fe, ni or Mo, and AC is acetate. The technical scheme specifically defines the sources of lithium, manganese and the modifying element, and it is understood that the sources of lithium, manganese and the modifying element can be other substances selected in the field by a person skilled in the art in combination with common knowledge in the field.
In a preferred embodiment, the organic complexing agent is at least one of citric acid, oxalic acid, glutamic acid, polypropylene glycol, PVDF and polyacrylamide. The technical scheme specifically limits the types of the organic complexing agents, and the organic complexing agents not only serve as complexing agents to enable metal ions to be uniformly distributed, but also serve as carbon sources to form a carbon coating layer, so that the full utilization of substances is achieved, and the pollution to the environment is reduced.
In a preferred embodiment, the controlling of the reaction temperature and the pH specifically includes: controlling the reaction temperature to be 40-100 ℃, and controlling the pH value to be 7-11. The technical scheme limits the reaction temperature and the pH value, and can be understood that the reaction temperature can also be any value within the ranges of 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and the pH value can also be any value within the ranges of 8, 9 and 10.
In a preferred embodiment, said N 2 /O 2 O in mixed atmosphere 2 The volume ratio of (A) to (B) is 0.85-1.0. The technical scheme specifically limits N 2 /O 2 O in mixed atmosphere 2 The volume ratio of (1) is O 2 Account for N 2 /O 2 The volume ratio of the mixed atmospheres, it being understood, can also be 0.90, 0.95, and any point within the range thereof.
In a preferred embodiment, the calcination temperature of the first stage calcination is 500-800 ℃, and the calcination time is 6-10h. The technical scheme specifically defines the calcination temperature and the calcination time of the first stage calcination, and it can be understood that the calcination temperature of the first stage calcination can also be 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ and any value within the range thereof, and the calcination time can also be 7h, 8h, 9h and any value within the range thereof.
In a preferred embodiment, the calcination temperature of the second stage calcination is 200-600 ℃, and the calcination time is 3-6h. The technical scheme specifically limits the calcining temperature and the calcining time of the second stage calcining, and can be understood that the calcining temperature of the second stage calcining can be any value within the ranges of 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ and the calcining time can be any value within the ranges of 4h, 5h and the calcining time.
In order to more clearly and specifically describe the double-modified lithium manganate material and the preparation method thereof provided by the embodiments of the present invention, the following description will be made with reference to specific examples.
Example 1
(1) Respectively weighing 11.32g, 88.68g and 1.50g of LiOH, mnAC and Al (NO) 3 ) 3 Dissolving in 500ml of deionized water, and marking as solution A;
(2) Weighing 112.02g of citric acid, and dissolving in 200ml of deionized water to obtain a solution B;
(3) Gradually adding the solution A into the solution B, and controlling the reaction temperature to be 65 ℃ and the pH value to be 8.5 until a gelatinous substance is generated;
(4) Drying and ball-milling the gel-like substance obtained in the step (3), then placing the powder material into a tube furnace for calcination, controlling the oxygen volume ratio in the atmosphere to be 0.86, keeping the temperature of the first-stage calcination at 650 ℃, and keeping the temperature for 8 hours; then annealing and cooling to 450 ℃, and preserving heat for 3h. Thus obtaining the surface carbon and aluminum oxide coated and aluminum doped double-modified lithium manganate material.
Example 2
(1) Respectively weighing 11.32g, 89.09g and 1.20g of LiOH and MnSO 4 、MgSO 4 Dissolving in 500ml of deionized water, and marking as solution A;
(2) Weighing 85.78g of glutamic acid, and dissolving in 200ml of deionized water to obtain a solution B;
(3) Gradually adding the solution A into the solution B, and controlling the reaction temperature at 50 ℃ and the pH value at 10 until a gel substance is generated;
(4) Drying and ball-milling the gel-like substance obtained in the step (3), then placing the powder material into a tube furnace for calcination, controlling the oxygen volume ratio in the atmosphere to be 0.92, keeping the primary calcination temperature to be 600 ℃, and keeping the temperature for 10 hours; then annealing and cooling to 500 ℃, and preserving heat for 4 hours. Thus obtaining the double-modified lithium manganate material with surface carbon and magnesium oxide coating and magnesium doping.
Comparative example 1
The preparation method of the modified lithium manganate material is the same as that of the double-modified lithium manganate material provided in example 1, except that the calcination atmosphere in comparative example 1 is air, so as to prepare an alumina-coated/aluminum-doped lithium manganate material.
Comparative example 2
The preparation method of the modified lithium manganate material is the same as that of the double-modified lithium manganate material provided in the above example 1, except that the solution A in the present comparative example 2 does not contain Al (NO) 3 ) 3 And preparing the carbon-coated lithium manganate material.
Comparative example 3
The preparation method of the modified lithium manganate material is the same as the preparation method of the double-modified lithium manganate material provided in the above example 2, except that in the present comparative example 3, the solution B is replaced by ethanol, so as to prepare the magnesium oxycarbide-coated magnesium-doped double-modified lithium manganate material.
Performance testing
The lithium manganate materials prepared in examples 1-2 and comparative examples 1-3 were used in lithium ion batteries: the active substance, the conductive agent and the binder are mixed according to the mass ratio of 8:1:1, coating the mixture on an aluminum foil to prepare an electrode slice, and performing vacuum drying; in a glove box under argon atmosphere, lithium metal is used as a counter electrode, liClO 4 EC/DEC is electrolyte, and a button cell is assembled for testing. The test conditions were: the test temperature is 50 ℃, the charge and discharge multiplying power is 1C, and the discharge cut-off voltage is 1.5V-4.5V (vs. Li) + /Li). The test results are shown in table 1 and fig. 2.
Table 1 electrochemical performance test results of lithium manganate materials in examples and comparative examples
Figure BDA0002927523590000081
As can be seen from the test results in table 1, compared with the comparative example, the double-modified lithium manganate material prepared by the present embodiment has good interface stability, reduces the occurrence of side reactions between electrodes/electrolytes at the interface, and simultaneously ensures the lithium ion transmission efficiency, and has good first charge-discharge efficiency and higher specific discharge capacity; meanwhile, the double-modification has good structural stability, inhibits lattice distortion and manganese dissolution, and improves the cycle stability of the material.
In addition, the above-mentioned embodiments are only examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention, and other variations or modifications may be made on the basis of the above description, which is not exhaustive, but still fall within the scope of the present invention.

Claims (6)

1. The double-modified lithium manganate material is characterized in that a metal element is doped in a double-modified lithium manganate material body, a metal oxide coating layer is arranged on the surface of the double-modified lithium manganate material body, and a carbon coating layer is arranged between the metal oxide coating layer and a main body material; the doping amount of the metal element is 1000ppm-10000 ppm;
the double-modified lithium manganate material is prepared by the following method:
preparing an aqueous solution containing lithium, manganese and modified elements in a certain proportion, and marking as a solution A;
preparing a solution of an organic complexing agent with a certain concentration, and marking as a solution B;
adding the solution A into the solution B, and controlling the reaction temperature and the pH value until a gel-like substance is obtained;
drying the gel-like material, ball milling, and adding N 2 /O 2 Carrying out first-stage calcination and second-stage calcination in a mixed atmosphere to obtain a double-modified lithium manganate material;
the metal element is at least one of Mg, al, cu, zr, ti, zn, fe, ni or Mo, and the metal oxide coating layer corresponds to: mgO and Al 2 O 3 、CuO、ZrO 2 、TiO 2 ZnO, feO, niO or MoO 3 At least one of (a);
the organic complexing agent is at least one of citric acid, oxalic acid and glutamic acid;
the calcining temperature of the first stage of calcining is 500-800 ℃, and the calcining time is 6-10 h;
the calcination temperature of the second stage of calcination is 200-450 ℃, and the calcination time is 3-6h.
2. The double-modified lithium manganate material according to claim 1, wherein the content of said metal oxide coating layer is 0.5-5wt% of said lithium manganate material being coated; the content of the carbon coating layer is 0.2-1wt% of the lithium manganate material to be coated.
3. The preparation method of the double-modified lithium manganate material according to any of claims 1 to 2, characterized by comprising the steps of:
preparing an aqueous solution containing lithium, manganese and modified elements in a certain proportion, and marking as a solution A;
preparing a solution of an organic complexing agent with a certain concentration, and marking as a solution B;
adding the solution A into the solution B, and controlling the reaction temperature and the pH value until a gel-like substance is obtained;
drying the gel-like material, ball milling, and adding N 2 /O 2 And carrying out first-stage calcination and second-stage calcination in a mixed atmosphere to obtain the double-modified lithium manganate material.
4. The method for preparing the double-modified lithium manganate material according to claim 3, wherein the source of lithium is at least one of lithium acetate, lithium carbonate, lithium hydroxide and lithium nitrate; the source of the manganese is at least one of manganese nitrate, manganese sulfate, manganese carbonate, manganese acetate and manganese oxide; the source of the modified element is MAC and MCO 3 、MOH、MNO 3 、MSO 4 M is Mg, al, cu, zr, ti, zn, fe, ni or Mo, and AC is acetate.
5. The preparation method of the double-modified lithium manganate material according to claim 3, wherein the controlling of the reaction temperature and the pH value is specifically: controlling the reaction temperature to be 40-100 ℃, and controlling the pH value to be 7-11.
6. According to claim 3The preparation method of the double-modified lithium manganate material is characterized in that N is 2 /O 2 O in mixed atmosphere 2 The volume ratio of (A) to (B) is 0.85-1.0.
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CN100547831C (en) * 2006-03-14 2009-10-07 深圳市比克电池有限公司 Modified spinelle manganic acid lithium material, preparation method and lithium secondary battery
CN103855384B (en) * 2014-03-25 2016-09-28 浙江美达瑞新材料科技有限公司 A kind of ternary cathode material of lithium ion battery of rare-earth-doped modification and preparation method thereof
CN106469810A (en) * 2016-08-31 2017-03-01 井冈山大学 Surface doping cladding process improves service life and the high-temperature behavior of LiMn2O4 system lithium cell
CN107994220A (en) * 2017-11-28 2018-05-04 广东工业大学 LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified
CN111799468B (en) * 2020-08-13 2022-02-25 中南大学 Lithium ion battery anode material jointly modified by ionic conductor and heterostructure, preparation method and application

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